Abstract
In this work, the kinetic and the mechanism of isothermal degradation of local chitin (CN), chitosan (CS) and the biocomposite Bentonite/Chitosan (5%Bt/CS) were investigated by thermogravimetric analysis in air atmosphere and in the temperatures range 285–330 °C. Fourier transform-infrared, X-ray diffractogram and differential scanning calorimetry analyses were used to determine the structure of the as prepared samples. DTG curves of the samples show that CN and CS presented one peak, while those of 5%Bt/CS presented one to three peaks as the isothermal degradation increases. This difference was linked to the strong interactions between CS and Bentonite, which improve the stability of CS in the biocomposite 5%Bt/CS. The common first DTG peak appearing in each sample was treated using the Friedman method, leading to the activation energy (Ea) of Ea(CN) = 127.18 kJ/mol > Ea(CS) = 103.90 kJ/mol > Ea(5%Bt/CS) = 80.64 kJ/mol. The auto-catalytic Sestak–Berggren model was found to be qualitatively matched the isothermal degradation process of each sample. The thermodynamic parameters show the appearance of an order in the activated complex with respect to the initial state and that the isothermal degradation process is endothermic and is not spontaneous.
Graphical Abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
Ahlafi H, Moussout H, Boukhlifi F et al (2013) Kinetics of N-deacetylation of chitin extracted from shrimp shells collected from coastal area of Morocco. Mediterr J Chem 2:503–513. https://doi.org/10.13171/mjc.2.3.2013.22.01.20
Alexandre M, Dubois P (2000) Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mater Sci Eng R Rep 28:1–63. https://doi.org/10.1016/S0927-796X(00)00012-7
Anitha A, Sowmya S, Kumar PTS et al (2014) Chitin and chitosan in selected biomedical applications. Prog Polym Sci 39:1644–1667. https://doi.org/10.1016/j.progpolymsci.2014.02.008
Arora S, Lal S, Kumar S et al (2011) Comparative degradation kinetic studies of three biopolymers: chitin, chitosan and cellulose. Arch Appl Sci Res 3:188–201
Baranwal A, Kumar A, Priyadharshini A et al (2018) Chitosan: an undisputed bio-fabrication material for tissue engineering and bio-sensing applications. Int J Biol Macromol 110:110–123. https://doi.org/10.1016/j.ijbiomac.2018.01.006
Barros SC, da Silva AA, Costa DB et al (2015) Thermal–mechanical behaviour of chitosan–cellulose derivative thermoreversible hydrogel films. Cellulose 22:1911–1929. https://doi.org/10.1007/s10570-015-0603-5
Boonchom B, Puttawong S (2010) Thermodynamics and kinetics of the dehydration reaction of FePO4·2H2O. Phys B Condens Matter 405:2350–2355. https://doi.org/10.1016/j.physb.2010.02.046
Boonchom B, Thongkam M (2010) Kinetics and thermodynamics of the formation of MnFeP4O12. J Chem Eng Data 55:211–216. https://doi.org/10.1021/je900310m
Branca C, D’Angelo G, Crupi C et al (2016) Role of the OH and NH vibrational groups in polysaccharide-nanocomposite interactions: a FTIR-ATR study on chitosan and chitosan/clay films. Polymer (United Kingdom) 99:614–622. https://doi.org/10.1016/j.polymer.2016.07.086
Cárdenas G, Anaya P, Von Plessing C et al (2008) Chitosan composite films. Biomedical applications. J Mater Sci Mater Med 19:2397–2405. https://doi.org/10.1007/s10856-007-3275-3
Chivrac F, Pollet E, Avérous L (2009) Progress in nano-biocomposites based on polysaccharides and nanoclays. Mater Sci Eng R Rep 67:1–17. https://doi.org/10.1016/j.mser.2009.09.002
Coats AW, Redfern JP (1964) Kinetic parameters from thermogravimetric data. Nature 201:68–69
Coats AW, Redfern JP (1965) Kinetics parameters from thermogravimetric data. II. Polym Lett 3:917–920. https://doi.org/10.1002/pol.1965.110031106
Corazzari I, Nisticò R, Turci F et al (2015) Advanced physico-chemical characterization of chitosan by means of TGA coupled on-line with FTIR and GCMS: thermal degradation and water adsorption capacity. Polym Degrad Stab 112:1–9. https://doi.org/10.1016/j.polymdegradstab.2014.12.006
Darder M, Colilla M, Ruiz-Hitzky E (2003) Biopolymer–clay nanocomposites based on chitosan intercalated in montmorillonite. Chem Mater 15:3774–3780. https://doi.org/10.1021/cm0343047
de Britto D, Campana-Filho SP (2007) Kinetics of the thermal degradation of chitosan. Thermochim Acta 465:73–82. https://doi.org/10.1016/j.tca.2007.09.008
Ehrlich H, Bazhenov VV, Debitus C et al (2017) Isolation and identification of chitin from heavy mineralized skeleton of Suberea clavata (Verongida: demospongiae: Porifera) marine demosponge. Int J Biol Macromol 104:1706–1712. https://doi.org/10.1016/j.ijbiomac.2017.01.141
Fan Q, Shan D, Xue H et al (2007) Amperometric phenol biosensor based on laponite clay–chitosan nanocomposite matrix. Biosens Bioelectron 22:816–821. https://doi.org/10.1016/j.bios.2006.03.002
Ferraro V, Cruz IB, Jorge RF et al (2010) Valorisation of natural extracts from marine source focused on marine by-products: a review. Food Res Int 43:2221–2233. https://doi.org/10.1016/j.foodres.2010.07.034
Friedman HL (1964) Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci Polym Symp 6:183–195. https://doi.org/10.1002/polc.5070060121
Gámiz-González MA, Correia DM, Lanceros-Mendez S et al (2017) Kinetic study of thermal degradation of chitosan as a function of deacetylation degree. Carbohydr Polym 167:52–58. https://doi.org/10.1016/j.carbpol.2017.03.020
Georgieva V, Zvezdova D, Vlaev L (2012) Non-isothermal kinetics of thermal degradation of chitosan. Chem Cent J 6:81. https://doi.org/10.1186/1752-153X-6-81
Giannakas A, Grigoriadi K, Leontiou A et al (2014) Preparation, characterization, mechanical and barrier properties investigation of chitosan–clay nanocomposites. Carbohydr Polym 108:103–111. https://doi.org/10.1016/j.carbpol.2014.03.019
Guinesi LS, Cavalheiro ÉTG (2006) The use of DSC curves to determine the acetylation degree of chitin/chitosan samples. Thermochim Acta 444:128–133. https://doi.org/10.1016/j.tca.2006.03.003
Günister E, Pestreli D, Ünlü CH et al (2007) Synthesis and characterization of chitosan–MMT biocomposite systems. Carbohydr Polym 67:358–365. https://doi.org/10.1016/j.carbpol.2006.06.004
Hao YH, Huang Z, Ye QQ et al (2017) A comparison study on non-isothermal decomposition kinetics of chitosan with different analysis methods. J Therm Anal Calorim 128:1077–1091. https://doi.org/10.1007/s10973-016-5972-y
Harish Prashanth KV, Kittur FS, Tharanathan RN (2002) Solid state structure of chitosan prepared under different N-deacetylating conditions. Carbohydr Polym 50:27–33. https://doi.org/10.1016/S0144-8617(01)00371-X
Hu Y, Tang L, Lu Q et al (2014) Preparation of cellulose nanocrystals and carboxylated cellulose nanocrystals from borer powder of bamboo. Cellulose 21:1611–1618. https://doi.org/10.1007/s10570-014-0236-0
Ibrahim M (2002) Preparation of cellulose and cellulose derivative azo compounds. Cellulose 9:337–349. https://doi.org/10.1023/A:1021154204053
Islam S, Bhuiyan MAR, Islam MN (2017) Chitin and chitosan: structure, properties and applications in biomedical engineering. J Polym Environ 25:854–866. https://doi.org/10.1007/s10924-016-0865-5
Kaya M, Dudakli F, Asan-Ozusaglam M et al (2016) Porous and nanofiber α-chitosan obtained from blue crab (Callinectes sapidus) tested for antimicrobial and antioxidant activities. LWT Food Sci Technol 65:1109–1117. https://doi.org/10.1016/j.lwt.2015.10.001
Khor E, Lim LY (2003) Implantable applications of chitin and chitosan. Biomaterials 24:2339–2349. https://doi.org/10.1016/S0142-9612(03)00026-7
Kissinger HE (1957) Reaction kinetics in differential thermal analysis. Anal Chem 29:1702–1706. https://doi.org/10.1021/ac60131a045
Kittur FS, Harish Prashanth KV, Udaya Sankar K, Tharanathan RN (2002) Characterization of chitin, chitosan and their carboxymethyl derivatives by differential scanning calorimetry. Carbohydr Polym 49:185–193. https://doi.org/10.1016/S0144-8617(01)00320-4
Kumar R, Majeti N (2000) A review of chitin and chitosan applications. React Funct Polym 46:1–27. https://doi.org/10.1016/S1381-5148(00)00038-9
Lamarque G, Viton C, Domard A (2004) Comparative study of the first heterogeneous deacetylation of α- and β-chitins in a multistep process. Biomacromolecules 5:992–1001. https://doi.org/10.1021/bm034498j
Le HR, Qu S, Mackay RE, Rothwell R (2012) Fabrication and mechanical properties of chitosan composite membrane containing hydroxyapatite particles. J Adv Ceram 1:66–71. https://doi.org/10.1007/s40145-012-0007-z
Li JM, Meng XG, Hu CW, Du J (2009) Adsorption of phenol, p-chlorophenol and p-nitrophenol onto functional chitosan. Bioresour Technol 100:1168–1173. https://doi.org/10.1016/j.biortech.2008.09.015
Montserrat S, Málek J, Colomer P (1998) Thermal degradation kinetics of epoxy–anhydride resins: I. Thermochim Acta 313:83–95. https://doi.org/10.1016/S0040-6031(97)00482-6
Moussout H, Ahlafi H, Aazza M, Bourakhouadar M (2016) Kinetics and mechanism of the thermal degradation of biopolymers chitin and chitosan using thermogravimetric analysis. Polym Degrad Stab 130:1–9. https://doi.org/10.1016/j.polymdegradstab.2016.05.016
Moussout H, Ahlafi H, Aazza M, Amechrouq A (2018) Bentonite/chitosan nanocomposite: preparation, characterization and kinetic study of its thermal degradation. Thermochim Acta 659:191–202. https://doi.org/10.1016/j.tca.2017.11.015
Nam YS, Park WH, Ihm D, Hudson SM (2010) Effect of the degree of deacetylation on the thermal decomposition of chitin and chitosan nanofibers. Carbohydr Polym 80:291–295. https://doi.org/10.1016/j.carbpol.2009.11.030
Nisticò R, Franzoso F, Cesano F et al (2017) Chitosan-derived iron oxide systems for magnetically guided and efficient water purification processes from polycyclic aromatic hydrocarbons. ACS Sustain Chem Eng 5:793–801. https://doi.org/10.1021/acssuschemeng.6b02126
Ou C-Y, Zhang C-H, Li S-D et al (2010) Thermal degradation kinetics of chitosan–cobalt complex as studied by thermogravimetric analysis. Carbohydr Polym 82:1284–1289. https://doi.org/10.1016/j.carbpol.2010.07.010
Park H, Choi B, Nguyen J et al (2013) Anionic carbohydrate-containing chitosan scaffolds for bone regeneration. Carbohydr Polym 97:587–596. https://doi.org/10.1016/j.carbpol.2013.05.023
Peniche-Covas C, Argüelles-Monal W, San Román J (1993) A kinetic study of the thermal degradation of chitosan and a mercaptan derivative of chitosan. Polym Degrad Stab 39:21–28. https://doi.org/10.1016/0141-3910(93)90120-8
Pillai CKS, Paul W, Sharma CP (2009) Chitin and chitosan polymers: chemistry, solubility and fiber formation. Prog Polym Sci 34:641–678. https://doi.org/10.1016/j.progpolymsci.2009.04.001
Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632. https://doi.org/10.1016/j.progpolymsci.2006.06.001
Rinaudo M, Pavlov G, Desbrières J (1999) Influence of acetic acid concentration on the solubilization of chitosan. Polymer (Guildf) 40:7029–7032. https://doi.org/10.1016/S0032-3861(99)00056-7
Roberts GAF (1992) Solubility and solution behaviour of Chitin and Chitosan. In: Roberts GAE (ed) Chitin chemistry. Palgrave, London, pp 274–329
Sagheer FAA, Al-Sughayer MA, Muslim S, Elsabee MZ (2009) Extraction and characterization of chitin and chitosan from marine sources in Arabian Gulf. Carbohydr Polym 77:410–419. https://doi.org/10.1016/j.carbpol.2009.01.032
Saheb N, Jog J (2015) Natural fiber polymer composites : a review. Adv Polym Technol 2329:351–363. https://doi.org/10.1002/(SICI)1098-2329(199924)18
Šesták J, Berggren G (1971) Study of the kinetics of the mechanism of solid-state reactions at increasing temperatures. Thermochim Acta 3:1–12. https://doi.org/10.1016/0040-6031(71)85051-7
Shukla SK, Mishra AK, Arotiba OA, Mamba BB (2013) Chitosan-based nanomaterials: a state-of-the-art review. Int J Biol Macromol 59:46–58. https://doi.org/10.1016/j.ijbiomac.2013.04.043
Signini R, Filho SPC (1999) On the preparation and characterization of chitosan hydrochloride. Polym Bull 42:159–166
Starink M (2003) The determination of activation energy from linear heating rate experiments: a comparison of the accuracy of isoconversion methods. Thermochim Acta 404:163–176. https://doi.org/10.1016/S0040-6031(03)00144-8
Stepniak I, Galinski MI, Nowacki K et al (2016) A novel chitosan/sponge chitin origin material as a membrane for supercapacitors-preparation and characterization. RSC Adv 6:4007–4013. https://doi.org/10.1039/c5ra22047e
Stolarek P, Ledakowicz S (2005) Pyrolysis kinetics of chitin by non-isothermal thermogravimetry. Thermochim Acta 433:200–208. https://doi.org/10.1016/j.tca.2005.03.012
Swetha M, Sahithi K, Moorthi A et al (2010) Biocomposites containing natural polymers and hydroxyapatite for bone tissue engineering. Int J Biol Macromol 47:1–4. https://doi.org/10.1016/j.ijbiomac.2010.03.015
Teli MD, Sheikh J (2012) Extraction of chitosan from shrimp shells waste and application in antibacterial finishing of bamboo rayon. Int J Biol Macromol 50:1195–1200. https://doi.org/10.1016/j.ijbiomac.2012.04.003
Topcu C, Caglar B, Onder A et al (2018) Structural characterization of chitosan–smectite nanocomposite and its application in the development of a novel potentiometric monohydrogen phosphate-selective sensor. Mater Res Bull 98:288–299. https://doi.org/10.1016/j.materresbull.2017.09.068
Vyazovkin S, Burnham AK, Criado JM et al (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19. https://doi.org/10.1016/j.tca.2011.03.034
Wang SF, Shen L, Tong YJ et al (2005) Biopolymer chitosan/montmorillonite nanocomposites: preparation and characterization. Polym Degrad Stab 90:123–131. https://doi.org/10.1016/j.polymdegradstab.2005.03.001
Wang Y, Chang Y, Yu L et al (2013) Crystalline structure and thermal property characterization of chitin from Antarctic krill (Euphausia superba). Carbohydr Polym 92:90–97. https://doi.org/10.1016/j.carbpol.2012.09.084
Wanjun T, Cunxin W, Donghua C (2005) Kinetic studies on the pyrolysis of chitin and chitosan. Polym Degrad Stab 87:389–394. https://doi.org/10.1016/j.polymdegradstab.2004.08.006
Wu T, Farnood R (2015) A preparation method of cellulose fiber networks reinforced by glutaraldehyde-treated chitosan. Cellulose 22:1955–1961. https://doi.org/10.1007/s10570-015-0609-z
Wysokowski M, Bazhenov VV, Tsurkan MV et al (2013) Isolation and identification of chitin in three-dimensional skeleton of Aplysina fistularis marine sponge. Int J Biol Macromol 62:94–100. https://doi.org/10.1016/j.ijbiomac.2013.08.039
Wysokowski M, Petrenko I, Stelling AL et al (2015) Poriferan chitin as a versatile template for extreme biomimetics. Polymers (Basel) 7:235–265. https://doi.org/10.3390/polym7020235
Xie DF, Martino VP, Sangwan P et al (2013) Elaboration and properties of plasticised chitosan-based exfoliated nano-biocomposites. Polymer (United Kingdom) 54:3654–3662. https://doi.org/10.1016/j.polymer.2013.05.017
Yin P, Tian Y, Wang Z et al (2011) Synthesis of functionalized silica gel with poly(diethylenetriamine bis(methylene phosphonic acid)) and its adsorption properties of transition metal ions. Mater Chem Phys 129:168–175. https://doi.org/10.1016/j.matchemphys.2011.03.067
Zheng LY, Zhu JF (2003) Study on antimicrobial activity of chitosan with different molecular weights. Carbohydr Polym 54:527–530. https://doi.org/10.1016/j.carbpol.2003.07.009
Zółtowska-Aksamitowska S, Shaala LA, Youssef DTA et al (2018) First report on chitin in a non-verongiid marine demosponge: the Mycale euplectellioides case. Mar Drugs 16:1–17. https://doi.org/10.3390/md16020068
Żółtowska-Aksamitowska S, Tsurkan MV, Lim SC et al (2018) The demosponge Pseudoceratina purpurea as a new source of fibrous chitin. Int J Biol Macromol 112:1021–1028. https://doi.org/10.1016/j.ijbiomac.2018.02.071
Acknowledgments
This work was supported by MESRSFC and CNRST-Rabat-Morocco, within the framework of the PPR2 project.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Moussout, H., Ahlafi, H., Aazza, M. et al. Kinetic and mechanism studies of the isothermal degradation of local chitin, chitosan and its biocomposite bentonite/chitosan. Cellulose 25, 5593–5609 (2018). https://doi.org/10.1007/s10570-018-1999-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-1999-5